EP3372998B1 - Sensor and method for measuring content of hydrogen in metal melt - Google Patents

Sensor and method for measuring content of hydrogen in metal melt Download PDF

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EP3372998B1
EP3372998B1 EP15908135.5A EP15908135A EP3372998B1 EP 3372998 B1 EP3372998 B1 EP 3372998B1 EP 15908135 A EP15908135 A EP 15908135A EP 3372998 B1 EP3372998 B1 EP 3372998B1
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metal melt
electrode
sensor
measured
hydrogen content
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EP3372998A1 (en
EP3372998A4 (en
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Ying Li
Yu shi DING
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Northeastern University China
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Northeastern University China
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/406—Cells and probes with solid electrolytes
    • G01N27/411—Cells and probes with solid electrolytes for investigating or analysing of liquid metals
    • G01N27/4112—Composition or fabrication of the solid electrolyte
    • G01N27/4114—Composition or fabrication of the solid electrolyte for detection of gases other than oxygen
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004—Gaseous mixtures, e.g. polluted air
    • G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
    • G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
    • G01N33/005—H2
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/301—Reference electrodes
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/20—Metals
    • G01N33/202—Constituents thereof
    • G01N33/2022—Non-metallic constituents
    • G01N33/2025—Gaseous constituents

Definitions

  • the present invention relates to a hydrogen measurement sensing technology, in particular to a sensor and measurement method for measuring hydrogen content in metal melt.
  • hydrogen is a harmful element in metal materials and can cause metal materials to produce defects such as hydrogen embrittlement, porosity and pinholes.
  • Timely measurement of hydrogen content in metals and proper dehydrogenation after information feedback can avoid various hydrogen-induced defects in metal materials.
  • EP0544281 TYK discloses a device for measuring hydrogen content in aluminum melt by a solid proton conductor.
  • the hydrogen content of the metal melt of 1000 DEG C or below such as aluminum melt can be measured.
  • the solid proton conductor hydrogen sensor can be used for measuring hydrogen content in gas
  • the reference electrode and the electrode to be measured of the solid proton conductor sensor are both external porous electrodes.
  • a reference compound with certain hydrogen partial pressure is stuffed into the reference electrode, or gas with certain hydrogen partial pressure is introduced, and the electrode to be measured is in contact with atmosphere to be measured, so that a concentration cell is obtained.
  • a potentiometer is used for measuring the electromotive force of the concentration cell.
  • the hydrogen partial pressure of the reference electrode is known (the hydrogen partial pressure of the reference electrode can be higher or lower than that of the electrode to be measured), so that the hydrogen partial pressure of the atmosphere to be measured can be calculated, and the hydrogen content is calculated.
  • a solid proton conductor is used as the main body of the sensor probe, the solid proton conductor and the metal melt are isolated by a ceramic bushing, a ceramic cover or a porous material, and thereof, a gas chamber is created between the proton conductor and the metal melt.
  • the hydrogen partial pressure of atmosphere in a porous material is equilibrium hydrogen partial pressure of the metal melt, and the hydrogen content in the aluminum melt can be obtained through calculation.
  • US2005/0252789 proposes that a metal-hydrogen material with stable chemical stability such as ⁇ Ti- ⁇ Ti, ⁇ Zr- ⁇ Zr and ⁇ Hf- ⁇ Hf is taken as the reference compound of the sensor.
  • the interface between the reference compound and the solid electrode can maintain chemical stability at higher temperature, influence of oxygen on the solid proton conductor is reduced, and stable hydrogen partial pressure is provided.
  • the patent does not refer to the measurement method of hydrogen content in detail.
  • US2009/0139876 discloses a device for measuring hydrogen content in metal melt by using a solid proton conductor and proposes a method for restoring the solid electrolyte of the proton conductor by using a water absorbing material such as AlN and BN.
  • the equilibrium hydrogen partial pressure established between the metal melt and the gas chamber in the probe is measured by using the hydrogen concentration cell of the solid proton conductor.
  • the method has the following disadvantages that: (1) time for establishing equilibrium between the metal melt and the gas chamber is long, which results in low sensor response speed; (2) the material for establishing the gas chamber in the sensor is usually the ceramic cover or fiber materials, water is easy to adhere to the surfaces of such materials, water reacts with the metal melt to produce a large amount of hydrogen during measurement, and the accuracy of measurement results is affected; and (3) during multiple measurement processes, the gas chamber is easy to block by metal and metal oxides adhered to the surface of the probe, so that establishment of equilibrium is slow, response speed is reduced and even measurement accuracy is affected. Further hydrogen sensors are known from EP2827137 A1 and JP2014160006 A .
  • the present invention provides a sensor and measurement for measuring hydrogen content in metal melt.
  • the invention is defined by the appended claims.
  • a proton conductor in the sensor is in direct contact with the metal melt to form an electrode to be measured. It is not necessary to establish hydrogen solubility equilibrium with the metal melt via gas for the electrode to be measured, but the proton conductor is adopted to directly establish electrochemical equilibrium between a reference compound and hydrogen in the metal melt.
  • a sensor for measuring hydrogen content in metal melt which comprises a solid proton conductor element, a reference electrode, a quasi-electrode to be measured, a reference compound, a through pipe and an insulating ceramic adhesive, wherein the through pipe and the solid proton conductor element are connected through the insulating ceramic adhesive to form an inner space, the surface located in the space, of the solid proton conductor element, is an inner surface, and the surface exposed outside is an outer surface; the reference porous electrode is coated to the inner surface of the solid proton conductor element, and the quasi-electrode to be measured is the outer surface of the solid proton conductor element; and the reference compound is gas, placed in the inner space and is in contact with the reference porous electrode.
  • the quasi-electrode to be measured is in contact with metal melt during hydrogen measurement, and the contact surface forms the electrode to be measured.
  • the sensor for measuring hydrogen content in metal melt also comprises gas guide pipe and a three-way clamp.
  • the reference compound is gas
  • the three-way clamp is connected with the upper part of the through pipe
  • the gas guide pipe is inserted into the inner space formed by the through pipe, the insulating ceramic adhesive and the solid proton conductor element through the three-way clamp and is connected to the reference porous electrode;
  • the bottom end of the gas guide pipe directly faces to the reference electrode and the solid proton conductor element, the bottom end of the gas guide pipe is a blind end, a side opening acts as a gas outlet which has the effect of preventing pressure change caused by the gas reference compound rushing at the reference porous electrode or the proton conductor element and improving measurement accuracy.
  • the sensor for measuring hydrogen content in metal melt can also comprise a reference electrode cable.
  • the reference electrode cable When the reference compound is a gas, the reference electrode cable is inserted into the through pipe through the three-way clamp, electrically connected with the reference porous electrode and externally connected to a measuring circuit; when, in examples not covered by the claimed invention, the reference compound is liquid or solid, a reference electrode cable penetrates through the insulating ceramic adhesive, is electrically connected with the reference porous electrode and is externally connected to the measuring circuit.
  • the gas guide pipe is made of corundum, quartz, zirconium oxide, stainless steel, nickel-chromium alloy or iron-chromium-aluminum alloy.
  • the sensor structure also comprises a reference electrode cable.
  • the three-way clamp is made of stainless steel, copper, Teflon, nylon or polyurethane.
  • the reference electrode cable is made of metal platinum, gold, silver, nickel-chromium alloy, iron-chromium-aluminum alloy or stainless steel.
  • the sensor structure for measuring hydrogen content in metal melt comprises an inert material of Al 2 O 3 , YSZ or Y 2 O 3 ; and the inert material is stuffed between the reference compound and the insulating ceramic adhesive.
  • the solid proton conductor element can adopt a tubular, spherical, flaky, discoid, cubic or cylindrical structure and is made of a perovskite or complex perovskite structure material.
  • the reference electrode is made of silver, platinum or gold.
  • the insulating ceramic adhesive is an alumina-based material.
  • the reference compound is gas, liquid or solid, wherein the gas comprises Ar-H 2 , N 2 -H 2 , He-H 2 , O 2 -H 2 O or N 2 -NH 3 gas doped or undoped with one or more inert gases, the liquid comprises Li-LiH, and the solid comprises Y-H, Ti-H Zr-H or Sc-H.
  • the insulating ceramic adhesive is used to seal the reference compound to the side of the reference electrode.
  • the through pipe is made of corundum, quartz, graphite, stainless steel, Theron, SiC or LaCrO 3 and acts as a support and a gas path.
  • f [H] is the activity coefficient of hydrogen in the metal melt
  • w [H] is the percentage by mass of hydrogen in the metal melt.
  • S 0 is the saturated solubility of hydrogen (ml/100 g), and K is a constant produced by unit transformation. Because the saturated solubility S 0 of most of metals is known thermodynamic data or thermodynamic data which can be calculated, the standard Gibbs free energy ⁇ G ⁇ for hydrogen dissolving in the metal melt can be calculated.
  • the standard Gibbs free energy ⁇ G ⁇ for hydrogen dissolving in the metal melt is only related to the kind and the temperature of the metal melt and does not change along with hydrogen content in the metal melt, when hydrogen is saturated in the metal melt, the standard Gibbs free energy ⁇ G ⁇ for hydrogen dissolving in the metal melt is the same as that in unsaturation.
  • the hydrogen content S of the metal melt can be calculated. According to different natures of the selected solid proton conductor and the metal melt to be measured, the formula (14) can be corrected according to experiment results.
  • the sensor and measurement method for measuring hydrogen content in metal melt disclosed by the present invention have the beneficial effects that
  • 1 Solid proton conductor element; 2. Reference porous electrode; 3. Gas guide pipe; 4. Insulating ceramic adhesive; 5. Through pipe; 6. Quasi-electrode to be measured; 7. Reference electrode cable; 8. Solid reference compound; 9. Inert material; 100. Electrode to be measured; 101. Metal melt to be measured; 102. Corrosion-resistant electrode; 103. Cable; 104. Three-way clamp; 105. Gas outlet; 106; Gas inlet.
  • the sensor for measuring hydrogen content in aluminum melt comprises a CaZr 0.9 In 0.1 O 3- ⁇ solid proton conductor element 1, a reference porous electrode 2, a quasi-electrode to be measured 6, a reference compound Ar-H 2 , a stainless steel gas guide pipe 3, a corundum through pipe 5, an alumina-based insulating ceramic adhesive 4 and a Teflon three-way clamp 104, wherein the solid proton conductor element 1 adopts a tubular structure and is made of perovskite, one end is sealed by the alumina-based insulating ceramic adhesive 4, the through pipe 5 and the solid proton conductor element 1 are connected through the insulating ceramic adhesive 4 to form an inner space, the surface located in the space, of the solid proton conductor element 1 is an inner surface, and the surface exposed outside is an outer surface; the reference porous electrode 2 is coated to the inner surface of the solid proton conductor element 1 and the alumina-based insulating ceramic adhesive 4, and the
  • the reference porous electrode is made of porous platinum.
  • the mole hydrogen content is 1.00%.
  • S 0 is the saturated solubility of hydrogen (ml/100 g), and K is a constant produced by unit transformation. Because the saturated solubility S 0 of most of metals is known thermodynamic data or thermodynamic data which can be calculated, the standard Gibbs free energy ⁇ G ⁇ for hydrogen dissolving in the metal melt can be calculated.
  • the standard Gibbs free energy ⁇ G ⁇ for hydrogen dissolving in the metal melt is only related to the kind and the temperature of the metal melt and does not change along with hydrogen content in the metal melt, when hydrogen is saturated in the metal melt, the standard free energy ⁇ G ⁇ for hydrogen dissolving in the metal melt is the same as that in unsaturation.
  • the sensor for measuring hydrogen content in aluminum melt is the same as that in the embodiment 1, as shown in Figure 3 .
  • the sensor structure also comprises a reference electrode cable 7 which is made of metal platinum.
  • the reference electrode cable 7 is inserted into the quartz through pipe 5 through the copper three-way clamp 104, is connected to the gold reference porous electrode 2 and is externally connected to a measuring circuit;
  • the gas guide pipe is made of corundum;
  • the solid proton conductor element 1 is made of CaZr 0.9 Sc 0.1 O 3- ⁇ ;
  • the three-way clamp 104 is made of copper;
  • the through pipe is made of quartz;
  • the reference porous electrode is made of porous gold.
  • the method for measuring hydrogen content in metal melt by using the sensor comprises the following process steps of (1) inserting the sensor and a graphite corrosion-resistant electrode into the aluminum melt of 750 DEG C, and making sure that the solid proton conductor element is fully immersed into the aluminum melt, the quasi-electrode to be measured is in direct contact with the metal melt and the contact surface is the electrode to be measured; (2) connecting a potentiometer and the reference electrode cable to the graphite corrosion-resistant electrode through a platinum wire, and measuring the potential difference between the reference electrode and the electrode to be measured; and (3) calculating the stabilized hydrogen content S of the metal melt according to the measured potential difference, the temperature of the metal melt and the saturated solubility of hydrogen in the metal melt to be 0.113ml/100gAl.
  • the sensor for measuring hydrogen content in aluminum melt is the same as that in the embodiment 1, as shown in Figure 4 .
  • the difference lies in that: the solid proton conductor element 1 used in the sensor structure adopts a flaky structure; the through pipe 5 is made of stainless steel; one end being contact with the proton conductor 1, of the nickel-chromium gas guide pipe 3 is a blind end, a side opening is used as a gas outlet, and the vertical distance between the gas outlet and the top end of the solid proton conductor is 2-5 mm; the gas guide material is made of nickel-chromium alloy; and the reference gas is He-H 2 , and the mole hydrogen content is 1.00%.
  • the method for measuring hydrogen content in metal melt by using the sensor comprises the following process steps of (1) inserting the sensor and a graphite corrosion-resistant electrode into the aluminum melt of 750 DEG C, and making sure that the solid proton conductor element is fully immersed into the aluminum melt, the quasi-electrode to be measured is in direct contact with the metal melt and the contact surface is the electrode to be measured; (2) connecting a potentiometer and the nickel-chromium gas guide pipe to the graphite corrosion-resistant electrode through a nickel-chromium wire, and measuring the potential difference between the reference electrode and the electrode to be measured; and (3) calculating the stabilized hydrogen content S of the aluminum melt according to the measured potential difference, the temperature of the metal melt and the saturated solubility of hydrogen in the metal melt to be 0.109ml/100gAl.
  • the sensor for measuring hydrogen content in aluminum melt is the same as that in the embodiment 3, as shown in Figure 5 .
  • the sensor structure also comprises a reference electrode cable 7 which is made of metal silver.
  • the reference electrode cable 7 is inserted into the through pipe 5 through the stainless steel clamp 104, is connected with the porous silver reference porous electrode 2 and is externally connected to a measuring circuit;
  • the through pipe 5 is made of quartz;
  • the gas guide pipe is made of corundum;
  • the reference porous electrode is made of porous silver;
  • the reference gas is N 2 -H 2 , and the mole hydrogen content is 1.00%.
  • the method for measuring hydrogen content in metal melt by using the sensor comprises the following process steps of (1) inserting the sensor and a graphite corrosion-resistant electrode into the aluminum melt of 750 DEG C, and making sure that the solid proton conductor element is fully immersed into the metal melt, the quasi-electrode to be measured is in direct contact with the metal melt and the contact surface is the electrode to be measured; (2) connecting a potentiometer and the reference electrode cable to the graphite corrosion-resistant electrode through a silver wire, and measuring the potential difference between the reference electrode and the electrode to be measured; and (3) calculating the stabilized hydrogen content S of the aluminum melt according to the measured potential difference, the temperature of the metal melt and the saturated solubility of hydrogen in the metal melt to be 0.130ml/100gAl.
  • the sensor for measuring hydrogen content in aluminum melt is the same as that in the embodiment 3, as shown in Figure 6 .
  • the difference lies in that: the solid proton conductor element 1 used in the sensor structure adopts a spherical structure.
  • the method for measuring hydrogen content in metal melt by using the sensor comprises the following process steps of (1) inserting the sensor and a graphite corrosion-resistant electrode into the aluminum melt of 750 DEG C, and making sure that the solid proton conductor element is fully immersed into the aluminum melt, the quasi-electrode to be measured is in direct contact with the metal melt and the contact surface is the electrode to be measured; (2) connecting a potentiometer and the gas guide pipe to the graphite corrosion-resistant electrode through a stainless steel wire, and measuring the potential difference between the reference electrode and the electrode to be measured; and (3) calculating the stabilized hydrogen content S of the aluminum melt according to the measured potential difference, the temperature of the metal melt and the saturated solubility of hydrogen in the metal melt to be 0.123ml/100gAl.
  • the sensor for measuring hydrogen content in aluminum melt is the same as that in the embodiment 5, as shown in Figure 7 .
  • the difference lies in that: the sensor structure also comprises a reference electrode cable 7 which is made of stainless steel.
  • the reference electrode cable 7 is inserted into the through pipe 5 through the Teflon three-way clamp 104, is connected to the reference porous electrode 2 and is externally connected to a measuring circuit; and the gas guide pipe is made of corundum.
  • the method for measuring hydrogen content in metal melt by using the sensor comprises the following process steps of (1) inserting the sensor and a graphite corrosion-resistant electrode into the aluminum melt of 750 DEG C, and making sure that the solid proton conductor element is fully immersed into the aluminum melt, the quasi-electrode to be measured is in direct contact with the metal melt and the contact surface is the electrode to be measured; (2) connecting a potentiometer and the reference electrode cable to the corrosion-resistant electrode through a stainless steel wire, and measuring the potential difference between the reference electrode and the electrode to be measured; and (3) calculating the stabilized hydrogen content S of the aluminum melt according to the measured potential difference, the temperature of the metal melt and the saturated solubility of hydrogen in the metal melt to be 0.099ml/100gAl.
  • the sensor for measuring hydrogen content in aluminum melt comprises a solid proton conductor element 1, a reference porous electrode 2, an electrode to be measured, a platinum-wire cable 7, a solid reference compound 8, a corundum through pipe 5, an alumina-based ceramic adhesive 4 and an Al 2 O 3 inert material 9, wherein the solid proton conductor element 1 adopts a tubular structure and is made of CaZr 0.9 In 0.1 O 3- ⁇ , one end is sealed by using the alumina-based ceramic adhesive 4, the through pipe 5 and the solid proton conductor element 1 are connected through the insulating ceramic adhesive 4 to form an inner space, the surface located in the inner space, of the solid proton conductor element 1 is an inner surface, and the surface exposed outside is an outer surface; the reference porous electrode 2 is coated to the inner surface of the solid proton conductor element 1, and the quasi-electrode 6 to be measured is the outer surface of the solid proton conductor element 1; the bottom of the solid proton conductor element 1 is stuffed with the Al 2
  • the reference porous electrode is made of platinum.
  • the reference compound is a Y-H system solid, and the mole hydrogen content in equilibrium atmosphere of the Y-H system solid at 750 DEG C is 0.11%.
  • the method for measuring hydrogen content in metal melt by using the sensor comprises the following process steps of (1) inserting the sensor and a graphite corrosion-resistant electrode into the aluminum melt of 750 DEG C, and making sure that the solid proton conductor element 1 is fully immersed into the metal melt, the quasi-electrode to be measured is in direct contact with the metal melt and the contact surface is the electrode to be measured; (2) connecting a potentiometer and a platinum-wire cable to the graphite corrosion-resistant electrode through a platinum wire, and measuring the potential difference between the reference electrode and the electrode to be measured; and (3) calculating the stabilized hydrogen content S of the aluminum melt according to the measured potential difference, the temperature of the metal melt and the saturated solubility of hydrogen in the metal melt to be 0.107ml/100gAl.
  • the sensor for measuring hydrogen content in aluminum melt is the same as that in the example 1, as shown in Figure 9 .
  • the difference lies in that: the solid proton conductor element 1 used in the sensor structure adopts a flaky structure and is made of CaZr 0.9 Sc 0.1 O 3- ⁇ ; the inert material is Y 2 O 3 ; the reference compound is a Sc-H system solid, and the mole hydrogen content in equilibrium atmosphere of the Sc-H system solid at 750 DEG C is 0.25%.
  • the method for measuring hydrogen content in metal melt by using the sensor comprises the following process steps of (1) inserting the sensor and a graphite corrosion-resistant electrode into the aluminum melt of 750 DEG C, and making sure that the solid proton conductor element is fully immersed into the aluminum melt, the quasi-electrode to be measured is in direct contact with the metal melt and the contact surface is the electrode to be measured; (2) connecting a potentiometer and a cable to the graphite corrosion-resistant electrode through a platinum wire, and measuring the potential difference between the reference electrode and the electrode to be measured; and (3) calculating the stabilized hydrogen content S of the aluminum melt according to the measured potential difference, the temperature of the metal melt and the saturated solubility of hydrogen in the metal melt to be 0.143ml/100gAl.

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Applications Claiming Priority (2)

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CN201510770945.6A CN105319253B (zh) 2015-11-12 2015-11-12 一种测量金属熔体中氢含量的传感器及测量方法
PCT/CN2015/096049 WO2017080005A1 (zh) 2015-11-12 2015-11-30 一种测量金属熔体中氢含量的传感器及测量方法

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CN106770518A (zh) * 2016-12-22 2017-05-31 东北大学 一种用于铝及铝合金熔体中的定氢装置及方法
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WO2021002199A1 (ja) * 2019-07-01 2021-01-07 東京窯業株式会社 固体基準物質及び水素ガスセンサ
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CN111024558B (zh) * 2019-12-24 2021-05-18 东北大学 一种测量铝熔体中氢扩散系数的装置及方法
US11549882B2 (en) * 2020-02-21 2023-01-10 The Regents Of The University Of Michigan Reference electrode and electrochemical monitoring system
CN111289405B (zh) * 2020-03-02 2022-07-01 哈尔滨理工大学 铝合金熔体氢分压惰性气体循环在线连续检测装置及其检测方法
CN112129824B (zh) * 2020-09-24 2021-11-30 东北大学 一种无损测量固体钢中氢含量的装置及方法
CN114324535B (zh) * 2022-01-05 2023-03-24 东北大学 一种可拆卸式金属熔体测氢传感器装置
CN114373559B (zh) * 2022-01-10 2024-09-27 中国原子能科学研究院 测定液态碱金属中的碳含量的系统及方法
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CN115856055B (zh) * 2022-12-06 2024-07-16 东北大学 一种测量镁熔体中氢含量的装置及方法
CN115825371B (zh) * 2022-12-06 2024-11-29 东北大学 一种测量金属中氢含量的装置及方法
CN119510529A (zh) * 2025-01-22 2025-02-25 浙江众氢科技有限公司 溶解氢的含量测量方法、测量装置以及计算机程序产品

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US10598629B2 (en) 2020-03-24
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JP2018533727A (ja) 2018-11-15
EP3372998A1 (en) 2018-09-12
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